Cosmetic composition containing at least one nonionic surface-active agent of the alkyl polyglycosides and/or polyglycerolated type and at least one crosslinked copolymer of maleic anhydride/ (C1 -C5) alkylvinyl ether

ABSTRACT

The invention relates to a cosmetic composition containing, in a cosmetically acceptable medium, at least one nonionic surface-active agent from the alkyl polyglycoside class and/or one polyglycerolated nonionic surface-active agent and at least one crosslinked copolymer of maleic anhydride/(C 1  -C 5 )alkyl vinyl ether, as well as to a cosmetic treatment process consisting in applying to keratinous matter a cosmetically effective quantity of this composition.

This is a continuation of application Ser. No. 08/709,664, filed Sep. 9,1996, now U.S. Pat. No. 5,146,147 which is a continuation of applicationSer. No. 08/607,204, filed Feb. 26, 1996, abandoned, which is acontinuation of application Ser. No. 08/214,423, filed Mar. 18, 1994,abandoned.

The invention relates to cosmetic compositions containing at least onenonionic surface-active agent of the alkyl polyglycoside and/orpolyglycerolated type and at least one crosslinked copolymer of maleicanhydride/(C₁ -C₅)alkyl vinyl ether.

The hydrolysed and neutralized crosslinked copolymer gels of maleicanhydride/(C₁ -C₅)alkyl vinyl ether are known as thickening agents or asstabilizing agents in aqueous or anhydrous cosmetic compositions for thecare or treatment of hair or skin. They are described in U.S. Pat. Nos.5,032,391, 5,034,220 and 5,024,779 from the company GAF.

Surface-active agents from the alkyl polyglycoside or polyglycerolatedclass have already been recommended in washing compositions for hair orskin. They are mild, well-tolerated and biodegradable detergents.

Hair, under attack from atmospheric agents such as light or chemicaltreatments, and washed with conventional washing bases, is difficult todisentangle, and this disadvantage is even more accentuated in the caseof fine hair.

Shampoo compositions which contain only nonionic surface-active agentsdo not lead to good cosmetic properties; in particular, thedisentangling of wet hair is difficult and the hair is coarse.

The applicant has just discovered, surprisingly, that the combination,in washing and/or treating compositions for keratinous matter, ofcrosslinked copolymers of maleic anhydride/(C₁ -C₅)alkyl vinyl etherwith specific nonionic surfactants of the alkyl polyglycoside typeand/or of the polyglycerolated type imparted considerably improveddisentangling properties on these compositions. Moreover, thecombination in accordance with the invention makes it possible to obtaina very mild foam, compared to the coarse foam which generally resultsfrom the use of nonionic agents.

In addition, the applicant has observed that compositions containingsuch a combination had good cosmetic properties such as softness and apleasant feel.

The subject of the present invention is thus cosmetic compositionscontaining at least one nonionic surface-active agent of alkylpolyglycoside and/or polyglycerolated type and at least one crosslinkedcopolymer of maleic anhydride/(C₁ -C₅)alkyl vinyl ether.

Another subject of the invention consists in the use of thesecompositions for treating and/or washing keratinous matter such as hairor skin.

Another subject of the invention relates to a process for the cosmetictreatment of hair or of the skin, using compositions in accordance withthe invention; the process for washing and treating hair beingparticularly preferred.

Other subjects of the invention will appear on reading the descriptionand the examples which follow.

The cosmetic compositions according to the invention contain, in acosmetically acceptable medium, at least one nonionic surface-activeagent of alkyl polyglycoside and/or polyglycerolated type and at leastone crosslinked copolymer of maleic anhydride/(C₁ -C₅)alkyl vinyl ether.The viscosity of an aqueous solution containing from 0.5 to 1.5% byweight of the said hydrolysed and neutralized copolymer, at a pH between4 and 11, measured at 25° C. using a BROOKFIELD RTV viscometer, with aspindle of the type TE at 10 revolutions/minute, is preferablyapproximately between 35,000 and 180,000 cps.

The crosslinked copolymers in accordance with the invention are preparedby polymerization of maleic anhydride, an alkyl vinyl ether and acrosslinking agent in the presence of a free radical initiator in asuitable solvent. A mixture of ethyl acetate and cyclohexane (35-55% byweight/45-65% by weight) is preferably used as a solvent.

The crosslinking agents are preferably used in proportions between 1 and5 mol % relative to the monoalkyl vinyl ether. They are, for example,chosen from unsaturated compounds such as aliphatic diol divinyl ethers;polyethylene glycol divinyl ethers; 1,7-octadiene; 1,9-decadiene;divinylbenzene; N,N'-methylenebisacrylamide; polyethylene glycoldiacrylate; trimethylolpropane triacrylate; propylene glycol diacrylate;polyol mono- or diacrylates; triallylamine; tetraallylethylenediamineand diallyl phthalate.

1,7-octadiene or 1,9-decadiene is more particularly used.

The free radical initiators are preferably used in proportions between0.001 and 1% by weight relative to the monomer composition. They are inparticular chosen from azobisisobutyronitrile, benzoyl peroxide, lauroylperoxide, caprylyl peroxide, acetyl peroxide, acetylbenzoyl peroxide,di-tert-butyl peroxide and azobis(2,4-dimethylvaleronitrile).

The polymerization is carried out at a temperature between 0 and 150°C., preferably between 50 and 100° C., and more particularly between 60and 80° C.

The crosslinked copolymers thus obtained are in powder form.

When they hydrolysed and neutralized in a basic aqueous solutioncontaining from 0.5 to 1.5% by weight of copolymer and a sufficientamount of a neutralizing agent such as a 10% alkali metal hydroxidesolution or a 30% aqueous ammonia solution, or of an alkanolamine suchas monoethanolamine, diethanolamine, triethanolamine,aminomethylpropanol or aminomethylpropanediol, the viscosity measuredwith the BROOKFIELD RTV viscometer, with a spindle of the type TE at 10revolutions/minute, at 25° C. and at a pH between 4 and 11, and inparticular between 6 and 7.4, is preferably between 35,000 and 180,000cps.

The copolymers which it is preferred to use according to the presentinvention are maleic anhydride/methyl vinyl ether copolymers crosslinkedwith 1 to 5 mol %, relative to the methyl vinyl ether, of 1,9-decadieneor of 1,7-octadiene.

An example of a commercially available product of this type is STABILEZE06 sold by the company ISP.

The crosslinked copolymers of the invention are present in the cosmeticcomposition in concentrations betwen 0.2 and 5% by weight, andpreferably between 0.3 and 3% by weight.

The alkyl polyglycosides which may be used in accordance with theinvention correspond in particular to the following formula (II):

    R(C.sub.6 H.sub.10 O.sub.5).sub.x --H                      (II)

corresponding to the structural formula (III): ##STR1## in which: Rdenotes one or a mixture of alkyl or alkenyl radicals having a straightor branched C₈ -C₂₄ chain; x is a number between 1 and 15.

The alkyl polyglycoside compounds of structural formula (III) definedabove, used in accordance with the invention, are preferably representedby the products sold by the company HENKEL under the name APG, such asthe products APG 300, APG 350, APG 500, APG 550, APG 625, APG base10-12; PLANTAREN 300, 600, 1200 CS/UP, 2000 CS/UP; the products sold bythe company SEPPIC under the names TRITON CG 110 (or ORAMIX CG 110) andTRITON CG 312 (or ORAMIX NS 10); those sold by the company BASF underthe name LUTENSOL GD 70.

The nonionic surface-active agents of the polyglycerolated type, used inaccordance with the present invention, are preferably chosen from thefollowing polyhydroxypropyl ether compounds:

(A) The compounds corresponding to the formula (IV): ##STR2## in whichthe group C₃ H₅ (OH)! represents the following structures, takentogether or separately: ##STR3## and R and n have one of the meaningsbelow:

a) R represents one or a mixture of C₁₀ -C₁₄ alkyl radicals and n is awhole or decimal number from 2 to 10, and preferably 3 to 6.

b) R represents a residue:

    R.sub.2 CONHCH.sub.2 --CH.sub.2 OCH.sub.2 --CH.sub.2 --    (V)

where R₂ denotes one or a mixture of C₁ -C₇ alkyl and/or alkenylradicals and n denotes a whole or decimal number from 1 to 5, andpreferably from 1.5 to 4.

c) R represents a residue:

    R.sub.3 --CHOH--CH.sub.2 --                                (VI)

where R₃ denotes a C₇ -C₂₁ aliphatic, cycloaliphatic or arylaliphaticradical and their mixtures, the aliphatic chains in particular denotingalkyl chains which may contain from 1 to 6 ether, thioether and/orhydroxymethylene groups and n denotes a whole or decimal number from 1to 10.

These surf actants of formula (IV) may be prepared according to theprocesses described in Patents FR 1,477,048, 2,328,763 and 2,091,516;

(B) The compounds prepared by acid-catalysed condensation of 2 to 10,and preferably of 2.5 to 6, moles of glycidol per mole of alcohol or ofalpha-diol containing 10 to 14 carbon atoms, at a temperature of 50 to120° C., glycidol being added slowly to the alcohol or to thealpha-diol. The process for the preparation of these compounds isdescribed in Patent FR-A-2,169,787;

(C) The polyhydroxypropyl ether compounds prepared by polyaddition ofglycerol monochlorohydrin with a polyhydroxylated organic compound inthe presence of a strong base, with progressive removal of the water bydistillation. These compounds are described in French PatentFR-A-2,574,786.

Among the nonionic surfactants of the polyhydroxypropyl ether classdescribed in paragraphs (A), (B) and (C) above, the preferred compoundsare represented by the formulae: ##STR4## where R₁ denotes a mixture ofC₁₀ H₂₁ and C₁₂ H₂₅ alkyl radicals;

(β) the compounds prepared by base-catalysed condensation of 3.5 molesof glycidol with an alpha-diol containing 12 carbon atoms, according tothe process described in Patent FR-A-2,091,516;

(γ) the compounds corresponding to the formula: ##STR5## where R₂denotes a mixture of radicals comprising the following alkyl and alkenylradicals: C₁₁ H₂₃, C₁₃ H₂₇, radicals derived from coconut fatty acidsand the radical derived from oleic acid;

(δ) the compounds prepared by condensation of 3.5 moles of glycidol witha mixture of C₁₁ -C₁₄ alpha-diols, described in Patent FR-A-2,091,516.

The polyhydroxypropyl ether nonionic surfactant obtained by condensationof glycerol monochlorohydrin (2.5 moles) in the presence of sodiumhydroxide with 1,2-dodecanediol is more particularly preferred.

If the compositions according to the invention are not used for washingkeratinous matter, the nonionic surface-active agent(s) of alkylpolyglycoside and/or polyglycerolated type is(are) used in suchcompositions in proportions between 0.1 and 5% by weight relative to thetotal weight of the composition. These compositions are in particularused as rinsing compositions, which are applied before or aftershampooing, colouring, bleaching, a permanent wave or a hairstraightening treatment, as a colouring or permanent waving composition.

If the compositions according to the invention are washing compositions,they contain the nonionic surfactant(s) of the alkyl polyglycosideand/or polyglycerolated type in proportions between 5 and 30% by weightrelative to the total weight of the composition, and more particularlybetween 5 and 20% by weight.

The pH of the compositions in accordance with the invention is generallybetween 2 and 9, more particularly between 3 and 6.

In so far as the cosmetically acceptable medium of the compositionaccording to the invention is an aqueous medium, it may consistexclusively of water or of a mixture of water and a cosmeticallyacceptable solvent, such as C₁ -C₄ lower alcohols like ethanol,isopropanol and n-butanol; alkylene glycols such as propylene glycol,and glycol ethers.

The compositions according to the invention may take the form of more orless thickened liquids, gels, emulsions (milks or creams),aqueous-alcoholic lotions, dispersions or aerosol foams.

The compositions are, for example, emollient lotions, milks or creams,lotions, milks or creams for the care of keratinous matter, creams ormilks for removing make-up, foundation bases, anti-sun lotions, milks orcreams, artificial tanning lotions, milks or creams, shaving creams orfoams, after-shave lotions, face masks, make-up products for the eyes,make-up powder and foundations for the face, nail varnishes, shampoos,bath or shower products, rinsing compositions for applying before orafter shampooing, colouring, bleaching, a permanent wave or a hairstraightening treatment.

The compositions in accordance with the invention may in additionoptionally contain various additives which do not alter the propertiesof the compositions, such as anionic, cationic, amphoteric orzwitterionic surface-active agents, nonionic surface-active agents otherthan those described above, anionic, nonionic, cationic or amphotericpolymers, proteins, hydrocarbon oils such as synthesis oils likeisoparaffins or inorganic, vegetable or animal oils, silicone oils,waxes, resins and/or gums, acidifying or basifying agents,preservatives, active agents, other thickeners, suspension-formingagents, softeners, sunscreen agents, perfumes, biocides, antioxidants,fluorine-containing compounds, pigments or other adjuvants commonly usedin cosmetics.

The compositions in accordance with the invention are applied to skin orto hair in a cosmetically effective quantity depending on the nature ofthe composition.

One specific application of the compositions according to the inventionis the application as a composition for the washing and cosmetictreating of keratinous matter, preferably of skin and hair, and moreparticularly as a a shampoo. In this case, the shampoo is applied to wetor dry hair in effective quantities to wash it, this application beingfollowed by a rinsing.

The examples which follow are intended to illustrate the inventionwithout in any way presenting a limiting character.

EXAMPLE 1

A shampoo is prepared having the following composition:

    ______________________________________    (C.sub.9 --C.sub.10 --C.sub.11 /20-40-40) alkyl                         10 g          AS    polyglycoside (1,4), sold at a    concentration of 50% of AS    under the name "APG 300" by the    company HENKEL    Maleic anhydride/methyl vinyl                         1.5 g    ether copolymer crosslinked with    1,9-decadiene (viscosity of a 0.5%    solution: 110,000 cps)    Triethanolamine lauryl sulphate                         5 g           AS    sold at a concentration of 40% of AS    Perfume, preservative                         qs    Sodium hydroxide     qs            pH = 7    Water                qs 100 g    ______________________________________

EXAMPLE 2

A shampoo is prepared having the following composition:

    ______________________________________    (C.sub.9 --C.sub.10 --C.sub.11 /20-40-40) alkyl                         10 g          AS    polyglycoside (1,4), sold at a    concentration of 50% of AS    under the name "APG 300" by the    company HENKEL    Maleic anhydride/methyl vinyl                         1.5 g    ether copolymer crosslinked with    1,9-decadiene (viscosity of a 0.5%    solution: 50,000 cps)    Perhydrosqualene     2 g    Perfume, preservative                         qs    Sodium hydroxide     qs            pH = 7    Water                qs 100 g    ______________________________________

EXAMPLE 3

A rinsing conditioner is prepared having the following composition:

    ______________________________________    (C.sub.9 --C.sub.10 --C.sub.11 /20-40-40) alkyl                          2 g           AS    polyglycoside (1,4), sold at a    concentration of 50% of AS    under the name "APG 300" by the    company HENKEL    Maleic anhydride/methyl vinyl                          1 g    ether copolymer crosslinked with    1,9-decadiene, sold under the name    "STABILEZE 06" by the company ISP.    Heptamethylnonane sold under the                          5 g    name "ARLAMOL HD" by the compnay ICI    Preservative, perfume qs    Sodium hydroxide      qs            pH = 6    Water                 qs 100 g    ______________________________________

EXAMPLE 4

A rinsing conditioner is prepared having the following composition:

    ______________________________________    (C.sub.9 --C.sub.10 --C.sub.11 /20-40-40) alkyl                          10 g          AS    polyglycoside (1,4), sold at a    concentration of 50% of AS    under the name "APG 300" by the    company HENKEL    Maleic anhydride/methyl vinyl                          1.75 g    ether copolymer crosslinked with    1,9-decadiene (viscosity of a 0.5%    solution: 110,000 cps)    Silk protein hydrolysate quater-                          3 g           AS    nized with cocyldimethylammonium    chloride, sold as an aqueous solution    containg 32% of AS under the name    "CROSILQUAT" by the company CRODA    Preservative, perfume qs    Sodium hydroxide      qs            pH = 7    Water                 qs 100 g    ______________________________________

EXAMPLE 5

A shampoo is prepared having the following composition:

    ______________________________________    Nonionic poly(hydroxypropyl ether)                          20 g    surfactant prepared by base-catalysed    condensation of 3.5 moles of glycidol    with a mixture of alphadiols containing    10 to 14 carbon atoms, according to    the process described in French    Patent No. 2,091,516    Maleic anhydride/methyl vinyl                          1 g    ether copolymer crosslinked with    1,9-decadiene (viscosity of a 0.5%    solution: 110,000 cps)    Perhydrosqualene      2 g    Preservative          qs    Sodium hydroxide      qs            pH = 5    Water                 qs 100 g    ______________________________________

EXAMPLE 6

A shampoo is prepared having the following composition:

    ______________________________________    (C.sub.9 --C.sub.10 --C.sub.11 /20-40-40) alkyl                           15 g          AS    polyglycoside (1,4), sold at a    concentration of 50% of AS    under the name "APG 300" by the    company HENKEL    Maleic anhydride/methyl vinyl                           1.5 g    ether copolymer crosslinked with    1,9-decadiene (viscosity of a 0.5%    solution: 50,000 cps)    Polydimethydiphenylsiloxane sold under                           3 g    the name "SILBIONE OIL 70641 V 200"    by the company RHONE POULENC    Preservative           qs    Sodium hydroxide       qs            pH = 6    Water                  qs 100 g    ______________________________________

EXAMPLE 7

A rinsing conditioner is prepared having the following composition:

    ______________________________________    (C.sub.9 --C.sub.10 --C.sub.11 /20-40-40) alkyl                           0.2 g         AS    polyglycoside (1,4), sold at a    concentration of 50% of AS    under the name "APG 300" by the    company HENKEL    Maleic anhydride/methyl vinyl                           5 g    ether copolymer crosslinked with    1,9-decadiene (viscosity of a 0.5%    solution: 110,000 cps)    Rapeseed oil           3 g    Preservative           qs    Sodium hydroxide       qs            pH = 4    Water                  qs 100 g    ______________________________________

EXAMPLE 8

A hair setting lotion is prepared having the following composition:

    ______________________________________    (C.sub.9 --C.sub.10 --C.sub.11 /20-40-40) alkyl                         0.1 g         AS    polyglycoside (1,4), sold at a    concentration of 50% of AS    under the name "APG 300" by the    company HENKEL    Maleic anhydride/methyl vinyl                         1 g    ether copolymer crosslinked with    1,9-decadiene, sold under the name    "STABILEZE 06" by the company ISP    by the company RHONE POULENC    Vinylpyrrolidone/vinyl acetate                         1 g    copolymer in alcoholic solution at    a concentration of 50% of AS    (PVP/VA E 735 from ISP)    2-Amino-2-methypropanol                         qs            pH = 7.5    Water                qs 100 g    ______________________________________

EXAMPLE 9

A shower gel is prepared having the following composition:

    ______________________________________    APG 300               15 g          AS    STABILEZE 06          2.5 g    Sodium lauryl ether sulphate                          8 g           AS    containing 2.2 moles of ethylene    oxide in an aqueous solution    containing 28% of AS    Acrylic acid/dimethyldiallyl-                          0.5 g         AS    ammonium chloride copolymer (20/80)    (Merquat 280 from Merck)    Preservative, perfume qs    NaOH                  qs            pH = 6.5    Water                 qs 100 g    ______________________________________

We claim:
 1. Cosmetic composition, containing, in a cosmeticallyacceptable medium, 0.1 to 30% by weight, relative to the total weight ofthe composition, of one or more nonionic alkyl polyglycosidesurface-active agent corresponding to the following structural formula:##STR6## in which R denotes alkyl radical having a straight or branchedC₈ -C₂₄ chain or mixtures thereof and x denotes a number between 1 and15, and between 0.2 and 5% by weight, relative to the total weight ofthe composition, of one or more crosslinked copolymer of maleicanhydride/(C₁ -C₅)alkyl vinyl ether,which is crosslinked with1,7-octadiene, the crosslinking agent comprising 1 to 5 mol % relativeto the monoalkyl vinyl ether.
 2. Composition according to claim 1,wherein the crosslinked copolymer of maleic anhydride/(C₁ -C₅)alkylvinyl ether dissolved in water at a concentration of 0.5 to 1.5%, whichcopolymer is hydrolysed and neutralized at a pH between 4 and 11, has aviscosity of approximately between 35,000 and 180,000 cps, measured at25° C. with a BROOKFIELD RTV viscometer, with a spindle of the type TEat 10 revolutions/minute.
 3. Composition according to claim 1, whereinthe cosmetically acceptable medium is an aqueous medium which consistsexclusively of water or of a mixture of water and a cosmeticallyacceptable solvent.
 4. Composition according to claim 1, wherein it isin it takes the form of a thickened liquid, a gel, an emulsion, anaqueous-alcoholic lotion, a dispersion or an aerosol foam. 5.Composition according to claim 1, further comprising anionic, cationic,amphoteric or zwitterionic surface-active agents, anionic, nonionic,cationic or amphoteric polymers, proteins, hydrocarbon oils, siliconeoils, waxes, resins or gums, acidifying or basifying agents,preservatives, active agents, other cosmetic thickeners,suspension-forming agents, softeners, sunscreen agents, perfumes,biocides, antioxidants, fluorine-containing compounds, pigments or otheradjuvants.
 6. Cosmetic treatment process, comprising applying to skin orto hair a cosmetically effective quantity of a composition according toclaim
 1. 7. Process for washing and cosmetically treating hair,comprising applying to wet or dry hair an effective quantity of thecomposition as described in claim 1 to wash the hair, and then rinsingwith water.
 8. Composition according to claim 1, wherein it containsbetween 0.3 and 3% by weight, relative to the total weight of thecomposition, of crosslinked copolymer.
 9. Composition according to claim1, wherein it contains 5 to 20% by weight, relative to the total weightof the composition, of the nonionic surface-active agent.